Caratterizzazione di membrane da nanofiltrazione

Nanofiltration (NF) is a pressure-driven membrane process, intermediate between reverse osmosis and ultrafiltration. Commercially available polymeric membranes have been used in a wide range of applications, such as drinking, process industry and waste water treatment. For all the applications requiring high stability and harsh washing procedures inorganic membranes are preferred due to their high chemical inertia. Typically, γ – Al2O3 as well as TiO2 and ZrO2 selective layers are used; the latter show higher chemical stability in a wide range of pH and temperatures. In this work the experimental characterization of two different type of membrane has been performed in order to investigate permeation properties, separation performance and efficiency with aqueous solutions containing strong inorganic electrolytes. The influence of salt concentration and feed pH as well as the role of concentration polarization and electrolyte type on the membrane behavior are investigated. Experimentation was performed testing a multi–layer structured NF membrane in α-Al2O3, TiO2 and ZrO2, and a polymeric membrane, in polyamide supported on polysulfone, with binary aqueous solutions containing NaCl, Na2SO4 or CaCl2; the effect of salt composition and pH in the feed side was studied both on flux and salt rejection. All the NF experimental data available for the two membranes were used to evaluate the volumetric membrane charge (X) corresponding to each operative conditions investigated, through the Donnan Steric Pore Model and Dielectric Exclusion (DSPM&DE). The results obtained allow to understand which are the main phenomena at the basis of the different behaviors observed.

Caratterizzazione di membrane inorganiche per la separazione di idrogeno da gas di reforming

The work of this thesis has been focused on the characterisation of inorganic membranes for the hydrogen purification from steam reforming gas. Composite membranes based on porous inorganic supports coated with palladium silver alloys and ceramic membranes have been analysed. A brief resume of theoretical laws governing transport of gases through dense and porous inorganic membranes and an overview on different methods to prepare inorganic membranes has been also reported. A description of the experimental apparatus used for the characterisation of gas permeability properties has been reported. The device used permits to evaluate transport properties in a wide range of temperatures (till 500°C) and pressures (till 15 bar). Data obtained from experimental campaigns reveal a good agreement with Sievert law for hydrogen transport through dense palladium based membranes while different transport mechanisms, such as Knudsen diffusion and Hagen-Poiseuille flow, have been observed for porous membranes and for palladium silver alloy ones with pinholes in the metal layer. Mixtures permeation experiments reveal also concentration polarisation phenomena and hydrogen permeability reduction due to carbon monoxide adsorption on metal surface.

Trasporto di materia in membrane polimeriche e nanocomposite per la separazione di gas

Membrane-based separation processes are acquiring, in the last years, an increasing importance because of their intrinsic energetic and environmental sustainability: some types of polymeric materials, showing adequate perm-selectivity features, appear rather suitable for these applications, because of their relatively low cost and easy processability. In this work have been studied two different types of polymeric membranes, in view of possible applications to the gas separation processes, i.e. Mixed Matrix Membranes (MMMs) and high free volume glassy polymers. Since the early 90’s, it has been understood that the performances of polymeric materials in the field of gas separations show an upper bound in terms of permeability and selectivity: in particular, an increase of permeability is often accompanied by a decrease of selectivity and vice-versa, while several inorganic materials, like zeolites or silica derivates, can overcome this limitation. As a consequence, it has been developed the idea of dispersing inorganic particles in polymeric matrices, in order to obtain membranes with improved perm-selectivity features. In particular, dispersing fumed silica nanoparticles in high free volume glassy polymers improves in all the cases gases and vapours permeability, while the selectivity may either increase or decrease, depending upon material and gas mixture: that effect is due to the capacity of nanoparticles to disrupt the local chain packing, increasing the dimensions of excess free volume elements trapped in the polymer matrix. In this work different kinds of MMMs were fabricated using amorphous Teflon® AF or PTMSP and fumed silica: in all the cases, a considerable increase of solubility, diffusivity and permeability of gases and vapours (n-alkanes, CO2, methanol) was observed, while the selectivity shows a non-monotonous trend with filler fraction. Moreover, the classical models for composites are not able to capture the increase of transport properties due to the silica addition, so it has been necessary to develop and validate an appropriate thermodynamic model that allows to predict correctly the mass transport features of MMMs. In this work, another material, called poly-trimethylsilyl-norbornene (PTMSN) was examined: it is a new generation high free volume glassy polymer that, like PTMSP, shows unusual high permeability and selectivity levels to the more condensable vapours. These two polymer differ each other because PTMSN shows a more pronounced chemical stability, due to its structure double-bond free. For this polymer, a set of Lattice Fluid parameters was estimated, making possible a comparison between experimental and theoretical solubility isotherms for hydrocarbons and alcoholic vapours: the successfully modelling task, based on application of NELF model, offers a reliable alternative to direct sorption measurement, which is extremely time-consuming due to the relevant relaxation phenomena showed by each sorption step. For this material also dilation experiments were performed, in order to quantify its dimensional stability in presence of large size, swelling vapours.